CN109192851A - A method of addition sintering aid prepares excellent electronic transport performance flexibility thermoelectricity thick-film material - Google Patents
A method of addition sintering aid prepares excellent electronic transport performance flexibility thermoelectricity thick-film material Download PDFInfo
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Abstract
The present invention relates to a kind of method that addition sintering aid prepares excellent electronic transport performance flexibility thermoelectricity thick-film material, which obtains mixed powder the following steps are included: 1) being uniformly mixed thermoelectric material powder and sintering aid；2) macromolecule resin is dissolved in solvent appropriate and obtains the solution of macromolecule resin；3) mixed powder is uniformly mixed with high-molecular resin solution and prepares thermoelectricity slurry；4) the thermoelectricity slurry is printed on substrate using printing process；5) it will be sintered after the slurry wet film levelling, drying.The present invention has the advantages that sintering aid environmental protection used is easy to get, it is cheap, the electronic transport performance of flexible thermoelectricity thick-film material can be significantly improved by the way that sintering aid is added, the preparation method of thermoelectricity thick-film material is simply controllable, short preparation period, it is suitable for industrialized production, is expected to the development of promotion face inner mold flexibility thermo-electric device.
Description
Technical field
The present invention relates to a kind of preparation methods of flexible thermoelectricity thick-film material, in particular to a kind of addition sintering aid prepares excellent
The method of different electronic transport performance flexibility thermoelectricity thick-film material.
Background technique
Thermoelectric material is a kind of new energy materials that thermal energy and electric energy may be implemented and directly convert, and is sent out in industrial exhaust heat thermoelectricity
The fields such as electricity, the power generation of solar generator-photoelectricity compound power-generating, deep space/deep-sea power supply, small temperature difference and thermoelectric cooling have important
Using.As microelectronics integrated device is widely used in high-power processor and terminal device, the heat dissipation of high power density hot spot
There is an urgent need to develop efficient thermal management schemes.Thermoelectric cooling technology based on thermoelectric material Peltier effect has structure letter
It is single, heat flow is big, high reliablity, starting are fast, movement-less part and it is small in size the advantages that, be to pay much attention to development in the world at present
Environmentally protective new refrigeration technologies.
According to the relationship between direction of heat flow and substrate, the typical structure of thermoelectric cooling device is divided into face appearance structure and face
Inner mold structure.Currently, the thermoelectric cooling device of business application comparative maturity is mainly face external form device, it is by block p-type and N-shaped
The thermoelectric element that thermoelectric arm is constituted is integrated in two in the form of electrically coupled in series and hot parallel connection and is electrically insulated and the good ceramics of heat transfer
Between plate, heat is transmitted along the direction perpendicular to ceramic substrate.But the thermo-electric device of this traditional structure usually flexibility is very
Difference, and requirement of the electronic device to refrigerator size when being difficult to meet integrated.Although having benefited from the development of micro-processing technology, this
Kind face external form thermoelectric cooling device is gradually developing towards micromation direction, but thermoelectricity arm lengths reduce bring temperature difference between the two ends
Decline to a great extent that the increase of accounting and the preparation of thermoelectricity thick-film material and micro Process be still in device all-in resistance with interface resistance
It is so the bottleneck of its further industrialization.Face inner mold device is prepared using the thermoelectric arm of film or bulk structure, hot-fluid side
To with substrate-parallel.The advantage of this structure is thermoelectricity brachium, is easy to establish the big temperature difference, interface resistance accounts in device all-in resistance
Than small, prepared by the film or thick-film technique that maturation can be used.Compared to thin film thermoelectric arm, the electricity of the thick film thermoelectric arm of same material
Resistance is smaller, advantageously reduces the resistance of entire device.
The preparation method of thermoelectricity thick film mainly have physical deposition, electrochemical deposition, cold pressing, dispensing printing, inkjet printing and
Silk-screen printing etc..Compared with physical deposition, electrochemical deposition and cold-press process, preparing thermoelectricity thick film using printing technology has system
Standby simple process, it is with short production cycle, be not necessarily to the advantages that high-accuracy complex instrument.However the thermoelectricity slurry of printing has to be added
Macromolecule resin just can guarantee the stability and printability of slurry, and the decomposition of subsequent heat treatment process bring organic matter is waved
The defects of hair can leave hole and crackle inside thick film, while the organic matter remained in thermoelectricity thick film can hinder carrier
It transports, the electrical property of thermoelectricity thick film is caused to deteriorate.Around this problem, correlative study person carries out the thick film after heat treatment cold etc.
Static pressure processing carries out hot-pressing processing during heat treatment, to improve its electronic transport performance, but is still unable to fully meet
The requirement of thermoelectric cooling device.Therefore, a kind of preparation side of flexible thermoelectricity thick-film material with excellent electronic transport performance is invented
Method is most important to the development for pushing face inner mold flexibility thermoelectric cooling device.
Summary of the invention
The object of the present invention is to provide a kind of addition sintering aids to prepare excellent electronic transport performance flexibility thermoelectricity thick-film material
Method, the preparation method can promote rearrangement and the mass transfer of thermoelectric granules, the consistency of thermoelectricity thick film be improved, so that it is defeated to improve its electricity
Transport performance.
To achieve the above object, present invention provide the technical scheme that a kind of 1 addition sintering aid prepares excellent electronic transport
The method of the flexible thermoelectricity thick-film material of energy, which is characterized in that the preparation method includes the following steps:
1) thermoelectric material powder and sintering aid are uniformly mixed and obtain mixed powder；
2) macromolecule resin is dissolved in solvent appropriate and obtains high-molecular resin solution；
2) mixed powder is uniformly mixed with high-molecular resin solution and prepares thermoelectricity slurry；
3) the thermoelectricity slurry is printed on substrate using printing process；
4) it will be sintered after the slurry wet film levelling, drying.
According to the above scheme, the sintering aid is fusing point in sintering temperature low-melting-point metal below, alloy or at least two-dimentional
Scale is in 100nm metal or alloy material below；The quality of the sintering aid is no more than thermoelectric material powder and sintering aid is mixed
Close the 10% of powder gross mass.
According to the above scheme, the low-melting-point metal is tin, bismuth, indium, and the low-melting alloy is SnBi system alloy, BiIn system
Alloy, SnBiIn system alloy, at least two-dimentional scale are bismuth nano-wire or nanometer in 100nm metal or alloy material below
Piece, antimony nano wire or nanometer sheet, bismuth telluride nano-wire or nanometer sheet, antimony telluride nano wire or nanometer sheet, nanowires of gold or nanometer
Piece, silver nanowires or nanometer sheet, copper nano-wire or nanometer sheet, nickel nano wire or nanometer sheet.
According to the above scheme, the thermoelectric material powder is p-type or N-shaped Bi2Te3Or Sb2Te3Base thermoelectricity material powder.
According to the above scheme, the macromolecule resin is epoxy resin, acrylic resin, polyurethane resin or cellulose tree
Rouge.
According to the above scheme, the solvent be ethyl alcohol, butyl glycidyl ether, terpinol and dimethyl ester in any one or
Their mixing.
According to the above scheme, curing agent, catalyst or other surfaces auxiliary agent are also contained in the high-molecular resin solution.
According to the above scheme, the printing is silk-screen printing, intaglio printing, inkjet printing or dispensing printing.
According to the above scheme, the substrate is polyimides, polyethylene terephthalate, polyethylene naphthalate
Or mica sheet.
According to the above scheme, the sintering temperature is between the fusing point of sintering aid and the tolerable temperature of substrate.
In above scheme, the sintering processes can using the pressurizing device of patent (publication number CN 107732000A) invention
To obtain preferably effect.
The mechanism of technical solution provided by the invention is: when the sintering aid of addition is that fusing point is below in heat treatment temperature
When metal or alloy, sintering aid can melt during heat treatment, form liquid phase, flow between thermoelectric granules and arrange again
Cloth, melting liquid phase are filled in the gap of thermoelectric granules, and after cooling, liquid metal or alloy solidify again, in thermoelectricity
The electronic transport path for being similar to " bridge " is formed between grain, to effectively improve the electronic transport performance of thermoelectricity thick film；When helping for addition
Burning agent is at least two-dimentional scale in 100nm metal or alloy material below, is brought using the big specific surface area of nano material
Special nano effect it can be made to melt or at least promote itself and thermoelectric material particle surface when sintering temperature is enough
Mass transfer, and then the consistency of thermoelectricity thick film is improved, reduce the contact resistance between thermoelectric granules, the final electricity for improving thermoelectricity thick film
Transport performance.
Compared with prior art, present invention has an advantage that under the action of sintering aid, thermoelectricity thick film can be significantly improved
Consistency and electronic transport performance, preparation method is simply controllable, and short preparation period is suitable for industrialized production.
Detailed description of the invention
Fig. 1 is the thermoelectricity composite thick film for not adding sintering aid and adding sn-bi alloy and the preparation of bismuth telluride nano-wire sintering aid
Surface SEM image.Wherein Fig. 1 a is the surface SEM image for not adding sintering aid (reference examples 1), and Fig. 1 b is 0.3% tin of addition
The surface SEM image of bismuth alloy (embodiment 1), Fig. 1 c are the surface SEM image for adding 1.5% sn-bi alloy (embodiment 2), figure
1d is the surface SEM image for adding 1% bismuth telluride nano-wire (embodiment 3), and Fig. 1 e is that 2% bismuth telluride nano-wire of addition (is implemented
Example 4) surface SEM image；
Fig. 2 be do not add sintering aid (reference examples 1) and addition sn-bi alloy (embodiment 1 and embodiment 2) and bismuth telluride receive
Relation curve between the conductivity and temperature of the thermoelectricity composite thick film of rice noodles sintering aid (embodiment 3 and embodiment 4) preparation；
Fig. 3 be do not add sintering aid (reference examples 1) and addition sn-bi alloy (embodiment 1 and embodiment 2) and bismuth telluride receive
Relationship between the Seebeck coefficient and temperature of the thermoelectricity composite thick film of rice noodles sintering aid (embodiment 3 and embodiment 4) preparation is bent
Line；
Fig. 4 be do not add sintering aid (reference examples 1) and addition sn-bi alloy (embodiment 1 and embodiment 2) and bismuth telluride receive
Relation curve between the power factor and temperature of the thermoelectricity composite thick film of rice noodles sintering aid (embodiment 3 and embodiment 4) preparation.
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
Embodiment 1
Add 0.3wt%Sn42Bi58Sintering aid prepares Bi0.5Sb1.5Te3Base thermoelectricity composite thick film, includes the following steps:
1) by p-type Bi0.5Sb1.5Te3The broken pure, grinding of crystal bar, crosses 120 mesh screens, obtains stand-by powder of the partial size less than 120 μm
Material；
2) it is calculated by mass percentage and weighs above-mentioned Bi0.5Sb1.5Te3Powder 9.97g and sintering aid Sn42Bi58Alloy
Powder 0.03g is added in high-energy ball milling tank, ratio of grinding media to material 55:1, and 50ml dehydrated alcohol is added as ball-milling medium, leads to after vacuumizing
Enter Ar atmosphere protection.Milling parameters are rotational speed of ball-mill 200r/min, and Ball-milling Time is for 24 hours；
3) powder after ball milling is centrifuged at revolving speed 4000r/min 10min, takes lower slurry, be dried in vacuo at 60 DEG C
It is dried in vacuo 2h in case, obtains containing 0.3wt%Sn42Bi58The mixed powder of sintering aid；
4) Bisphenol F diglycidyl ether epoxy resin 0.25g, methyl hexahydrophthalic anhydride 0.2125g, 2- ethyl -4- first are weighed
Base imidazoles 0.03g, butyl glycidyl ether 0.6263g prepare the solution of epoxy resin, mixed with above-mentioned mixed powder 3.94g,
After being dispersed with stirring, uniform and stable Bi is obtained0.5Sb1.5Te3Base thermoelectricity slurry；
5) polyimide substrate for cutting suitable dimension is cleaned by ultrasonic 5min in dehydrated alcohol, obtains stand-by base after dry
Then above-mentioned thermoelectricity slurry is printed on substrate by plate using silk screen print method.Thick film after printing places 15min at room temperature
After be put into vacuum oven, the dry 1h at 100 DEG C is dried and uncured thick-film material；
6) the thermoelectricity thick film after above-mentioned drying is placed in the pressurizing mold of patent (CN 107732000A) invention, will be added
Device after pressure is placed in tube furnace, vacuumizes ventilation, is finally heat-treated under Ar protective atmosphere, heat treatment temperature 300
DEG C, heat treatment time 4h, 5 DEG C/min of heating rate obtain fine and close Bi after hot pressed sintering0.5Sb1.5Te3Base thermoelectricity thick film.
The thermoelectricity thick film of above-mentioned preparation is subjected to Surface Microstructure characterization and thermoelectricity capability test, is as a result listed in figure respectively
1b and Fig. 2~4.From surface, SEM image be can be seen that compared with the thermoelectricity thick film (see Fig. 1 a) for being not added with sintering aid preparation, be added
Add 0.3wt%Sn42Bi58The Bi of sintering aid preparation0.5Sb1.5Te3Base thermoelectricity composite thick film surface is more flat and smooth, hole and splits
Line is reduced, and compactness significantly improves.From Fig. 2~4 as can be seen that compared with being not added with thermoelectricity thick film prepared by sintering aid, addition
0.3wt%Sn42Bi58The Bi of sintering aid preparation0.5Sb1.5Te3The conductivity of base thermoelectricity composite thick film is by 1.61 × 104S·m-1Increase
Greatly to 3.54 × 104S·m-1, conductivity improves 120%；Seebeck coefficient is declined, from 251 μ VK-1Drop to 234 μ
V·K-1；Finally, power factor is significantly improved, from 1.10mWK-2·m-1Increase to 1.95mWK-2·m-1, improve
77%.
Embodiment 2
Add 1.5wt%Sn42Bi58Sintering aid prepares Bi0.5Sb1.5Te3Base thermoelectricity composite thick film, includes the following steps:
By p-type Bi0.5Sb1.5Te3The broken pure, grinding of crystal bar, crosses 120 mesh screens, obtains stand-by powder of the partial size less than 120 μm
Material；
It is calculated by mass percentage and weighs above-mentioned Bi0.5Sb1.5Te3Powder 9.85g and sintering aid Sn42Bi58Alloyed powder
0.15g is added in high-energy ball milling tank, ratio of grinding media to material 55:1, and 50ml dehydrated alcohol is added as ball-milling medium, is passed through after vacuumizing
Ar atmosphere protection.Milling parameters are rotational speed of ball-mill 200r/min, and Ball-milling Time is for 24 hours；
Powder after ball milling is centrifuged 10min at revolving speed 4000r/min, takes lower slurry, in 60 DEG C of vacuum ovens
Middle vacuum drying 2h is obtained containing 1.5wt%Sn42Bi58The mixed powder of sintering aid；
Weigh Bisphenol F diglycidyl ether epoxy resin 0.25g, methyl hexahydrophthalic anhydride 0.2125g, 2- ethyl -4- methyl
Imidazoles 0.03g, 0.6263g butyl glycidyl ether prepares the solution of epoxy resin, mixes, stirs with above-mentioned mixed powder 3.94g
After mixing dispersion, uniform and stable Bi is obtained0.5Sb1.5Te3Base thermoelectricity slurry；
The polyimide substrate for cutting suitable dimension is cleaned by ultrasonic 5min in dehydrated alcohol, obtains stand-by base after dry
Then above-mentioned thermoelectricity slurry is printed on substrate by plate using silk screen print method.Thick film after printing places 15min at room temperature
After be put into vacuum oven, the dry 1h at 100 DEG C is dried and uncured thick-film material；
Thermoelectricity thick film after above-mentioned drying is placed in the pressurizing mold of patent (CN 107732000A) invention, will be pressurizeed
Device afterwards is placed in tube furnace, vacuumizes ventilation, is finally heat-treated under Ar protective atmosphere, and 300 DEG C of heat treatment temperature,
Heat treatment time 4h, 5 DEG C/min of heating rate obtain fine and close Bi after hot pressed sintering0.5Sb1.5Te3Base thermoelectricity thick film.
The thermoelectricity thick film of above-mentioned preparation is subjected to Surface Microstructure characterization and thermoelectricity capability test, is as a result listed in figure respectively
1c and Fig. 2~4.From surface, SEM image be can be seen that compared with the thermoelectricity thick film (see Fig. 1 a) for being not added with sintering aid preparation, be added
Add 1.5wt%Sn42Bi58The Bi of sintering aid preparation0.5Sb1.5Te3Base thermoelectricity composite thick film surface is more flat and smooth, hole and splits
Line is reduced, and compactness significantly improves.From Fig. 2~4 as can be seen that compared with being not added with thermoelectricity thick film prepared by sintering aid, addition
1.5wt%Sn42Bi58The Bi of sintering aid preparation0.5Sb1.5Te3The conductivity of base thermoelectricity composite thick film significantly improves, by 1.61 ×
104S·m-1Increase to 5.98 × 104S·m-1, conductivity improves 271%；Seebeck coefficient is decreased obviously, from 251 μ VK-1
Drop to 146 μ VK-1；Finally, power factor is improved, from 1.10mWK-2·m-1Increase to 1.26mWK-2·m-1, improve 15%.
Embodiment 3
It adds 1wt% bismuth telluride nano-wire sintering aid and prepares Bi0.5Sb1.5Te3Base thermoelectricity composite thick film, including walk as follows
It is rapid:
1) Bi is prepared2Te3Nano wire
Weigh 0.1g SDS, 0.0183g Na2TeO3With 0.0150g NaBH4, it is successively dissolved in 100mL under magnetic stirring
In water, uniform solution is formed, under the conditions of ice-water bath, by Na2TeO3And NaBH4Solution is added dropwise in SDS solution and constantly stirs
It mixes, solution gradually becomes black, obtains the dispersion liquid of Te crystal seed；
By 1g PVP K90 and 0.25g Na2TeO3It is dissolved in 70mL water, obtains clear solution under magnetic stirring, with
10mL Te crystal seed dispersion liquid and 1.5mL hydrazine hydrate solution move into the stainless steel cauldron that liner is polytetrafluoroethylene (PTFE), are placed in height
72h is kept the temperature at 145 DEG C in warm furnace, is cooled to room temperature to reaction kettle, is centrifuged, washs to obtain Te nano wire；
By 0.233g Bi (NO3)3, 0.1g NaOH and 1g PVP K30 be dissolved in 80mL water, add Te nanometers above-mentioned
Line is uniformly mixed, and is moved into the stainless steel cauldron that liner is polytetrafluoroethylene (PTFE), and 2mL hydrazine hydrate is then added, and closing is anti-
Kettle is answered, 48h should be kept the temperature down at 140 DEG C by being placed in high temperature furnace, obtain Bi2Te3The dispersion liquid of nano wire；
It is cooled to room temperature to reaction kettle, after ultrasonic disperse is uniform, measures 20ml, after centrifuge washing is dry, weigh gained powder
Last quality is 0.025g (for determining the Bi mixed with thermoelectricity powder2Te3The dosage of nanowire dispersion)；
2) Bi is prepared0.5Sb1.5Te3Base thermoelectricity composite thick film
By p-type Bi0.5Sb1.5Te3The broken pure, grinding of crystal bar, crosses 120 mesh screens, obtains stand-by powder of the partial size less than 120 μm
Material weighs powder 9.9g, and 80ml Bi is added2Te3Nanowire dispersion, capping kettle are placed in high temperature furnace at 120 DEG C
Keep the temperature 10h；After reaction kettle is cooled to room temperature, bismuth telluride nano-wire containing 1wt% sintering aid is centrifuged, washed, being dried in vacuo and to obtain
Mixed powder；
Weigh Bisphenol F diglycidyl ether epoxy resin 0.25g, methyl hexahydrophthalic anhydride 0.2125g, 2- ethyl -4- methyl
Imidazoles 0.03g, 0.6263g butyl glycidyl ether prepares the solution of epoxy resin, mixes, stirs with above-mentioned mixed powder 3.94g
After mixing dispersion, uniform and stable Bi is obtained0.5Sb1.5Te3Base thermoelectricity slurry；
The polyimide substrate for cutting suitable dimension is cleaned by ultrasonic 5min in dehydrated alcohol, obtains stand-by base after dry
Above-mentioned thermoelectricity slurry is printed on substrate by plate using silk screen print method, and the thick film after printing is placed 15min at room temperature and put again
Enter vacuum oven, the dry 1h at 100 DEG C is dried and uncured thick-film material；
Thermoelectricity thick film after above-mentioned drying is placed in the pressurizing mold of patent (CN 107732000A) invention, will be pressurizeed
Device afterwards is placed in tube furnace, vacuumizes ventilation, is finally heat-treated under Ar protective atmosphere, and 300 DEG C of heat treatment temperature,
Heat treatment time 4h, 5 DEG C/min of heating rate obtain fine and close Bi after hot pressed sintering0.5Sb1.5Te3Base thermoelectricity thick film.
The thermoelectricity thick film of above-mentioned preparation is subjected to Surface Microstructure characterization and thermoelectricity capability test, is as a result listed in figure respectively
1d and Fig. 2~4.From surface, SEM image be can be seen that compared with the thermoelectricity thick film (see Fig. 1 a) for being not added with sintering aid preparation, be added
The Bi for adding 1wt% bismuth telluride nano-wire sintering aid to prepare0.5Sb1.5Te3Base thermoelectricity composite thick film surface is more flat and smooth, hole
It is reduced with crackle, compactness significantly improves.From Fig. 2~4 as can be seen that compared with being not added with thermoelectricity thick film prepared by sintering aid,
Add the Bi of 1wt% bismuth telluride nano-wire sintering aid preparation0.5Sb1.5Te3The conductivity of base thermoelectricity composite thick film by 1.61 ×
104S·m-1Increase to 1.81 × 104S·m-1, conductivity improves 14%；Seebeck coefficient is basically unchanged；Finally, power because
Son is from 1.10mWK-2·m-1Increase to 1.23mWK-2·m-1, improve 14%.
Embodiment 4
It adds 2wt% bismuth telluride nano-wire sintering aid and prepares Bi0.5Sb1.5Te3Base thermoelectricity composite thick film, including walk as follows
It is rapid:
Bi is prepared with embodiment 32Te3Nanowire dispersion；
Bi after weighing ball milling0.5Sb1.5Te3160ml Bi is added in powder 9.8g2Te3Nanowire dispersion, capping
Kettle is placed in high temperature furnace and keeps the temperature 10h at 120 DEG C；After reaction kettle is cooled to room temperature, after centrifugation, washing, vacuum drying, obtain
To the mixed powder of the sintering aid of bismuth telluride nano-wire containing 2wt%；
Weigh Bisphenol F diglycidyl ether epoxy resin 0.25g, methyl hexahydrophthalic anhydride 0.2125g, 2- ethyl -4- methyl
Imidazoles 0.03g, 0.6263g butyl glycidyl ether configures the solution of epoxy resin, with the sintering aid of bismuth telluride nano-wire containing 2wt%
Mixed powder 3.94g mixing, be dispersed with stirring after, obtain uniform and stable Bi0.5Sb1.5Te3Base thermoelectricity slurry；
The polyimide substrate for cutting suitable dimension is cleaned by ultrasonic 5min in dehydrated alcohol, obtains stand-by base after dry
Then above-mentioned thermoelectricity slurry is printed on substrate by plate using silk screen print method.Thick film after printing places 15min at room temperature
After be put into vacuum oven, the dry 1h at 100 DEG C is dried and uncured thick-film material；
Thermoelectricity thick film after above-mentioned drying is placed in the pressurizing mold of our patent early period (CN 107732000A) inventions
In, the device after pressurization is placed in tube furnace, ventilation is vacuumized, is finally heat-treated under Ar protective atmosphere, is heat-treated
300 DEG C of temperature, heat treatment time 4h, 5 DEG C/min of heating rate, fine and close Bi is obtained after hot pressed sintering0.5Sb1.5Te3Base thermoelectricity
Thick film.
The thermoelectricity thick film of above-mentioned preparation is subjected to Surface Microstructure characterization and thermoelectricity capability test, is as a result listed in figure respectively
1e and Fig. 2~4.From surface, SEM image be can be seen that compared with the thermoelectricity thick film (see Fig. 1 a) for being not added with sintering aid preparation, be added
The Bi for adding 2wt% bismuth telluride nano-wire sintering aid to prepare0.5Sb1.5Te3Base thermoelectricity composite thick film surface is more flat and smooth, hole
It is reduced with crackle, compactness significantly improves.From Fig. 2~4 as can be seen that compared with being not added with thermoelectricity thick film prepared by sintering aid,
Add the Bi of 2wt% bismuth telluride nano-wire sintering aid preparation0.5Sb1.5Te3The conductivity of base thermoelectricity composite thick film by 1.61 ×
104S·m-1Increase to 2.41 × 104S·m-1, improve 50%；Seebeck coefficient is basically unchanged；Finally, power factor from
1.10mW·K-2·m-1Increase to 1.62mWK-2·m-1, improve 47%.
Reference examples 1:Bi0.5Sb1.5Te3Base thermoelectricity material
By the broken pure, grinding of p-type bismuth telluride crystal bar, 120 mesh screens are crossed, stand-by powder of the partial size less than 120 μm is obtained；
Weigh Bi0.5Sb1.5Te3Powder 10g is added in high-energy ball milling tank, ratio of grinding media to material 55:1, and 50ml dehydrated alcohol is added
As ball-milling medium, Ar atmosphere protection is passed through after vacuumizing, milling parameters are rotational speed of ball-mill 200r/min, Ball-milling Time
24h；
Powder after ball milling is centrifuged 10min at revolving speed 4000r/min, takes lower slurry, in a vacuum drying oven 60
DEG C empty dry 2h, obtains Bi0.5Sb1.5Te3Powder；
Weigh Bisphenol F diglycidyl ether epoxy resin 0.25g, methyl hexahydrophthalic anhydride 0.2125g, 2- ethyl -4- methyl
Imidazoles 0.03g, butyl glycidyl ether 0.6263g configure the solution of epoxy resin, with Bi0.5Sb1.5Te3Powder 3.94g mixing,
After being dispersed with stirring, uniform and stable Bi is obtained0.5Sb1.5Te3Base thermoelectricity slurry；
The polyimide substrate for cutting suitable dimension is cleaned by ultrasonic 5min in dehydrated alcohol, obtains stand-by base after dry
Then above-mentioned thermoelectricity slurry is printed on substrate by plate using silk screen print method, the thick film after printing places 15min at room temperature
After be put into vacuum oven, the dry 1h at 100 DEG C is dried and uncured thick-film material；
Thermoelectricity thick film after above-mentioned drying is placed in the pressurizing mold of our patent early period (CN 107732000A) inventions
In, the device after pressurization is placed in tube furnace, ventilation is vacuumized, is finally heat-treated under Ar protective atmosphere, is heat-treated
300 DEG C of temperature, heat treatment time 4h, 5 DEG C/min of heating rate, Bi is obtained after hot pressed sintering0.5Sb1.5Te3Base thermoelectricity thick film.
The thermoelectricity thick film of above-mentioned preparation is subjected to Surface Microstructure characterization and thermoelectricity capability test, is as a result listed in figure respectively
1a and Fig. 2~4.From surface, SEM image can be seen that the thermoelectricity thick film for being not added with sintering aid preparation and add appropriate sn-bi alloy
Or bismuth telluride nano-wire is compared for the thermoelectricity thick film of sintering aid, is not added with the Bi of sintering aid preparation0.5Sb1.5Te3Base thermoelectricity is compound
Thick film surface is relatively rough, and hole and crackle are more, and compactness is poor.From Fig. 2~4 as can be seen that with adding prepared by sintering aid
Thermoelectricity thick film is compared, and thermoelectricity thick film conductivity and the power factor for being not added with sintering aid preparation are all lower, and electronic transport performance is poor.
Claims (10)
1. a kind of method that addition sintering aid prepares excellent electronic transport performance flexibility thermoelectricity thick-film material, which is characterized in that described
Preparation method includes the following steps:
1) thermoelectric material powder and sintering aid are uniformly mixed and obtain mixed powder；
2) macromolecule resin is dissolved in solvent appropriate and obtains high-molecular resin solution；
2) mixed powder is uniformly mixed with high-molecular resin solution and prepares thermoelectricity slurry；
3) the thermoelectricity slurry is printed on substrate using printing process；
4) it will be sintered after the slurry wet film levelling, drying.
2. preparation method as described in claim 1, which is characterized in that the sintering aid is that fusing point is below low in sintering temperature
Melting point metals, alloy or at least two-dimentional scale are in 100nm metal or alloy material below；The quality of the sintering aid is no more than
The 10% of thermoelectric material powder and sintering aid mixed powder gross mass.
3. preparation method as claimed in claim 2, which is characterized in that the low-melting-point metal is tin, bismuth, indium, the eutectic
Point alloy is SnBi system alloy, BiIn system alloy, SnBiIn system alloy, and at least two-dimentional scale is in 100nm metal below
Or alloy material is bismuth nano-wire or nanometer sheet, antimony nano wire or nanometer sheet, bismuth telluride nano-wire or nanometer sheet, antimony telluride nanometer
Line or nanometer sheet, nanowires of gold or nanometer sheet, silver nanowires or nanometer sheet, copper nano-wire or nanometer sheet, nickel nano wire or nanometer
Piece.
4. preparation method as described in claim 1, which is characterized in that the thermoelectric material powder is p-type or N-shaped Bi2Te3Or
Sb2Te3Base thermoelectricity material powder.
5. preparation method as described in claim 1, which is characterized in that the macromolecule resin is epoxy resin, acrylic acid tree
Rouge, polyurethane resin or celluosic resin.
6. preparation method as described in claim 1, which is characterized in that the solvent is ethyl alcohol, butyl glycidyl ether, pine tar
The mixing of any one or they in pure and mild dimethyl ester.
7. preparation method as described in claim 1, which is characterized in that in the high-molecular resin solution also containing curing agent,
Catalyst or other surfaces auxiliary agent.
8. preparation method as described in claim 1, which is characterized in that described print is beaten for silk-screen printing, intaglio printing, ink-jet
Print or dispensing printing.
9. preparation method as described in claim 1, which is characterized in that the substrate is polyimides, poly terephthalic acid second
Diol ester, polyethylene naphthalate or mica sheet.
10. preparation method as described in claim 1, which is characterized in that fusing point and base of the sintering temperature between sintering aid
Between the tolerable temperature of plate.
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| CN111276598A (en) * | 2020-03-20 | 2020-06-12 | 北京航空航天大学杭州创新研究院 | Printed bismuth telluride film suitable for wide temperature range and preparation method thereof |
| CN112234137A (en) * | 2020-10-30 | 2021-01-15 | 武汉理工大学 | Large-area flexible thermoelectric refrigeration thin film cascade device and preparation method thereof |
| CN113725348A (en) * | 2021-08-10 | 2021-11-30 | 武汉理工大学 | Flexible thermoelectric and electromagnetic energy conversion film with enhanced refrigeration performance and preparation method thereof |
| CN114316676A (en) * | 2021-12-09 | 2022-04-12 | 武汉大学 | Printing ink for preparing thermoelectric device and method for preparing thermoelectric device by using printing ink |
| EP4131436A4 (en) * | 2020-03-23 | 2024-03-13 | Proterial Ltd | Method for producing thermoelectric conversion element |
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| CN113725348A (en) * | 2021-08-10 | 2021-11-30 | 武汉理工大学 | Flexible thermoelectric and electromagnetic energy conversion film with enhanced refrigeration performance and preparation method thereof |
| CN114316676A (en) * | 2021-12-09 | 2022-04-12 | 武汉大学 | Printing ink for preparing thermoelectric device and method for preparing thermoelectric device by using printing ink |
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